Quantum chemical calculations of electronically excited states: formamide, its protonated form and alkali cation complexes as case studies |
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Authors: | Ivana Antol Mario Barbatti Mirjana Eckert-Maksić Hans Lischka |
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Affiliation: | (1) Division of Organic Chemistry and Biochemistry, Rudjer Bošković Institute, Zagreb, Croatia;(2) Institute for Theoretical Chemistry, University of Vienna, Vienna, Austria |
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Abstract: | The properties of formamide, its protonated form and interaction complexes with lithium and sodium cations were studied in electronically excited singlet states by means of high-level multireference ab initio methods. The vertical excitation energies show a marked influence on protonation with particular large effects found for the O-protonated form as compared to neutral formamide. Complexation with Li+ and Na+ leads to a pronounced shift of the nO–π* state to higher energies while the π–π* state moves in opposite direction. Geometry optimizations in the lowest excited singlet show strong geometrical effects leading to pyramidalization at the N and C atoms. The photodynamical simulations performed for formamide in the first excited singlet state show that the main primary deactivation path is CN dissociation with a lifetime of about 420?fs. |
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Keywords: | Photochemistry Basicity Absorption Metal ion affinities Multireference configuration interaction. |
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